CN1012570B - Process for treating ammonium nitrate-centg. waste water - Google Patents

Process for treating ammonium nitrate-centg. waste water

Info

Publication number
CN1012570B
CN1012570B CN86102728A CN86102728A CN1012570B CN 1012570 B CN1012570 B CN 1012570B CN 86102728 A CN86102728 A CN 86102728A CN 86102728 A CN86102728 A CN 86102728A CN 1012570 B CN1012570 B CN 1012570B
Authority
CN
China
Prior art keywords
waste water
thermolysis
oxygen
wet method
ruthenium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CN86102728A
Other languages
Chinese (zh)
Other versions
CN86102728A (en
Inventor
原田吉明
沖野贞造
土井康史
松浦広元
山崎健一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Osaka Gas Co Ltd
Original Assignee
Osaka Gas Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP60064227A external-priority patent/JPH0645025B2/en
Priority claimed from JP60064228A external-priority patent/JPH0645026B2/en
Priority claimed from JP60064229A external-priority patent/JPH0647100B2/en
Application filed by Osaka Gas Co Ltd filed Critical Osaka Gas Co Ltd
Publication of CN86102728A publication Critical patent/CN86102728A/en
Publication of CN1012570B publication Critical patent/CN1012570B/en
Expired legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • B01J27/045—Platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • B01J27/13—Platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/025—Thermal hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/06—Treatment of sludge; Devices therefor by oxidation
    • C02F11/08—Wet air oxidation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00—Liquid purification or separation
    • Y10S210/902—Materials removed
    • Y10S210/903—Nitrogenous

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Catalysts (AREA)

Abstract

This invention provides a process for treating ammonium nitrate-containing waste water which comprises subjecting the waste water to wet thermal decomposition in the presence of a catalyst supported by a carrier and containing as an active component at least one of precious metals and compounds thereof insoluble or sparingly soluble in water while maintaining the waste water at a pH of about 3 to about 11.5 and a temperature of about 100 DEG to about 370 DEG C.

Description

Process for treating ammonium nitrate-centg. waste water
The present invention addresses the treatment process that contains ammonium nitrate wastewater.
Recent years, from the viewpoint of water quality control, remove nitrogenous composition (particularly " ammonia-state nitrogen ") in the waste water and available chemical process oxidation material (hereinafter note do " COD＜chemical oxygen demand (COD)〉component) seem important further.
We have carried out long-term and extensive studies to the treatment process of ammonia-containing water, thereby proposed the treatment process of simple and easy and economically feasible ammonia-containing water, these methods are normally under the specified condition and having in the presence of the special catalyzer waste water is carried out wet oxidation process (the promptly Japanese communique 19757/1984 of speciallyying permit; 42992/1981; 42391/1982; 27999/1983; Disclosed method such as No. 33320/1982).
Recently because the nuclear power ratio in the energy industry increases the weight of day by day, the important techniques problem that we faced be exactly to the pre-treatment of uranium ore and used uranium fuel aftertreatment produced contains NH 4NO 3Waste water is handled.We attempt to adopt the treatment process (below be called " existing method ") of above-mentioned ammonia-containing water to handle this NH of containing 4NO 3Waste water, and find existing method decomposing N H extremely effectively + 4Ion, but can effective satisfactorily decomposing N O - 3Ion.This shortcoming estimates it may is because NH 4NO 3Excessive concentration (reaching 1% to 10% approximately, i.e. 10000ppm to 100000ppm) causes.
In order to overcome above-mentioned shortcoming, we have carried out deep research again, concurrent present anaerobic or being lower than in the presence of the oxygen of theoretical requirement, to containing NH 4NO 3Waste water carry out the wet method thermolysis, rather than adopt the oxygen be higher than the theory demands amount to carry out the waste water wet oxidation with prior art, can make NO - 3Ion image NH + 4Ion is the same, also can be decomposed effectively, and said here theoretical amount oxygen is meant the required oxygen of ammonia component, organism and inorganics that decomposes in this waste water.We continue studies have shown that, when carrying out the wet method thermolysis in the presence of the oxygen that is being lower than theoretical requirement, contain NH 4NO 3Waste water in to add mol ratio be 1＜NH + 4-N/NO - 3Behind the ammonia of-N≤5, the decomposition efficiency of each component can be further improved.By we also find behind the big quantity research,, contain NH being lower than in the presence of the oxygen of theoretical requirement 4NO 3Waste water in added COD component and NO - 3The ionic mol ratio is not more than at 1 o'clock, and waste water is carried out the wet method thermal decomposition process, NH wherein + 4And NO - 3Ion all can be decomposed effectively; And this NH that contains 4NO 3Waste water in be 1＜NH in molar ratio + 4-N/NO - 3-N≤5 add ammonia, and COD component and NO - 3The ionic mol ratio is not more than at 1 o'clock, makes it stand the wet method thermolysis being lower than in the presence of the oxygen of theoretical amount, this moment NH + 4And NO - 3Ionic decomposes more effective.Or rather, the invention provides five kinds of method of wastewater treatment:
(1) contains the ammonium nitrate wastewater facture, this method is to have in anaerobic in the presence of the catalyzer of carrier institute carrier band, keep the pH value about 3 to about 11.5 of waste water and make it that wet method thermolysis take place about 100 to about 370 ℃ temperature range, it is insoluble or be slightly soluble in the active ingredient of the compound of water as it that catalyzer wherein contains at least a precious metal or its.
(2) contain the ammonium nitrate wastewater facture, this method is to carry out waste water wet method pyrolysated under the following conditions: (ⅰ) in the presence of the catalyzer by carrier institute carrier band, it is insoluble or be slightly soluble in the active ingredient of the compound of water as it that this catalyzer contains a kind of precious metal or its at least; (ⅱ) be lower than in the presence of the oxygen of theoretical requirement, the oxygen of said theoretical requirement is meant the ammonia in the waste water, organism and inorganics is resolved into N 2, H 2O and CO 2Required oxygen amount makes the pH value of waste water maintain about 3 to about 11.5 simultaneously, and temperature is approximately 100 to about 370 ℃.
(3) contain the facture of ammonium nitrate wastewater, this method comprises that adding mol ratio in this waste water is 1＜NH + 4-N/NO - 3The ammonia of-N≤5 makes waste water stand the wet method thermolysis under the following conditions: (ⅰ) in the presence of carrier carried catalyzer, this catalyzer contains the insoluble or compound that is slightly soluble in water of at least a precious metal or its as active ingredient; (ⅱ) be lower than in the presence of the oxygen of theoretical requirement, the oxygen of this theory requirement is meant the ammonia in the waste water, organism and inorganics is decomposed into N 2, H 2O and CO 2Required oxygen amount makes the pH value of waste water maintain about 3 to about 11.5 simultaneously, and temperature is about 100 to about 370 ℃.
(4) contain the treatment process of ammonium nitrate wastewater, this method comprises in waste water adds and NO - 3The ionic mol ratio is not more than 1 COD component, and waste water carried out the wet method thermolysis, its condition is: (ⅰ) in the presence of carrier carried catalyzer, this catalyzer contains the insoluble or compound that is slightly soluble in water of at least a precious metal or its as its active ingredient; (ⅱ) be lower than in the presence of the oxygen of theoretical requirement, the oxygen of theoretical requirement is meant the ammonia in the waste water, organism and inorganics is decomposed into N 2, H 2O and CO 2Required oxygen amount makes the pH value of waste water maintain about 3 to about 11.5 simultaneously, and temperature is about 100 to about 370 ℃.
(5) contain the treatment process of ammonium nitrate wastewater, this method comprises adds every mol NO in waste water - 3Ion is not more than 1 mole COD component and adds its mol ratio is 1＜NH + 4-N/NO - 3The ammonia of-N≤5 makes waste water stand the wet method thermolysis, and its condition is: (ⅰ) in the presence of the catalyzer by carrier institute carrier band, this catalyzer contains the insoluble or compound that is slightly soluble in water of at least a precious metal or its as its active ingredient; (ⅱ) be lower than in the presence of the oxygen of theoretical requirement, the oxygen of this theory requirement is meant that with the ammonia in the waste water, organism and inorganics are decomposed into N 2, H 2O and CO 2Required oxygen amount makes the pH of waste water maintain about 3 to about 11.5 simultaneously, and temperature is about 100 to about 370 ℃.
In whole specification sheets and appending claims, used " theoretical amount " speech about oxygen is meant that all " with existing ammonia in the waste water, organism and inorganics are decomposed into N 2, H 2O and CO 2Required theoretical oxygen amount ", " NH + 4-N " and " NO - 3-N " be meant ammonia-state nitrogen respectively " and " nitric nitrogen ".
Can comprise with the waste water that the present invention's method is handled and contain NH 4NO 3Various waste water, its NH 4NO 3Content is preferably up to 1% or higher.In the waste water that needs to handle, can contain organism and inorganic substance with the present invention's method.When pH about 3 to about 11.5, preferably about 5 to about 11 when implementing present method, can obtain high-level efficiency.Therefore, in case of necessity, the pH available hydrogen sodium oxide of waste water, yellow soda ash, alkaline matters such as calcium hydroxide are regulated.
The active ingredient of catalyst system therefor of the present invention can be a ruthenium, rhodium, palladium, osmium, iridium, platinum and gold and these metals water insoluble or be slightly soluble in the compound of water.These active ingredients can use separately, and perhaps wherein at least two mixing are used.Useful compound insoluble or that be slightly soluble in water has ruthenous chloride, platinum dichloride, sulfuration ruthenium, rhodium sulphide etc.These active ingredients of catalyzer all are according to a conventional method by carrier carried and use, and used carrier has titanium dioxide, zirconium white, aluminum oxide, silicon-dioxide, alumina silica, gac and porous metal bodies etc., porous metal bodies such as nickel, nickel-chromium, nickel-chromium-aluminium, nickel-chromium-iron or the like.The amount of carrier carried active constituent is about 0.05 to about 25%, about 0.5 to about 3% better (all calculating with vehicle weight).Used catalyzer can be a pearl, ball shape, column, fragment, granular or other any desired shapes.If used reaction column is a kind of fixed bed, then the air speed of waste water is approximately 0.5 to 10 liter/hour, preferably about 1 to about 5 liters/hour (all calculating with free column volume).The size of granules of catalyst or fragment is generally about 3 to about 50 millimeters, preferably about 5 to about 25 millimeters on the used carrier of fixed bed.Under the situation of fluidized-bed, the catalyzer of used carrier band preferably is suspended in it makes a kind of pulpous state liquid in waste water, its consumption is to form a kind of fluidized-bed in reactor, promptly calculate by formed suspension, its consumption is generally about 0.5 to about 20%(weight), be preferably about 0.5 to about 10%(weight).Fluidized-bed is when actual motion, preferably the catalyzer with carrier band adds in the reactor with the dilute slurry that is suspended in the waste water, through reaction and treated water utilizes sedimentation, method centrifugal or that other are suitable that catalyzer is therefrom told, isolated catalyzer is reused.For ease of isolating catalyzer in the waste water of handling certainly, used its globule size of carried catalyst preferably about 0.15 of fluidized-bed is to about 0.5 millimeter.
When the present invention's method be having be lower than theoretical oxygen demand in the presence of when implementing, available multiple gases is made oxygen source.For example, gas commonly used among the present invention has air, oxygen-rich air, and oxygen contains oxygen waste gas etc., may contain one or more following impurity in these waste gas: as prussic acid, hydrogen sulfide, ammonia, sulfur oxide, organic sulfide, nitrogen oxide, hydrocarbon etc.The feeding speed of oxygen-containing gas is according to decomposing contained ammonia in the waste water, the theoretical amount oxygen that organism and inorganics are required and changing.In general, the feeding amount of gas approximately is 0.2 to 0.6 times of theoretical oxygen amount in the reaction system.When containing oxygen waste gas and make oxygen source, the oxious component in the gas can be converted into innoxious substance simultaneously with contained objectionable impurities in the waste water.Oxygen-containing gas can be from a position or two or several position feed reactor.
Usually, reaction is to carry out at about 100 to about 370 ℃, preferably carries out to about 300 ℃ temperature about 200.Temperature of reaction is higher, NH + 4Ion and NO - 3It is also higher that ionic is eliminated efficient, and the residence time of waste water in reactor is also shorter, yet facility investment is also higher.Therefore, temperature of reaction will be according to the waste water type, processing requirements, operation and composite factor such as cost of equipment and determine.Therefore, the required pressure of reaction only need make waste water can keep its liquid state at least under predetermined temperature.
When containing NH 4NO 3Waste water be 1＜NH in molar ratio + 4-N/NO - 3-N≤5 have added when carrying out the wet method pyrolysis behind the ammonia, and reaction conditions is same as described above.
When containing NH 4NO 3Waste water in by every mole of NO - 3Ion adds the COD component be not more than 1 mole when carrying out the wet method pyrolysis, and reaction conditions is identical with above-mentioned condition.Every mole of NO in the waste water - 3The dosage for the treatment of of COD component be preferably about 0.1 to about 0.5 mole.
When containing NH 4NO 3Waste water in add with above-mentioned COD component and mol ratio with amount be 1＜NH + 4-N/NO - 3When the ammonia of-N≤5 carried out the wet method pyrolysis, reaction conditions was also with above-mentioned identical.
The COD component of adding in the waste water and the source of ammonia can comprise the various waste water that contain these materials, as the gas liquor that coking plant, producer gas plant and coal liquefaction plant produced, the waste water that these factories are produced in used gas purification process, sweetening process and remove cyanogen (change thing) waste water that process produced, oily(waste)water, the waste water that sludge activation, the active slurry process of deposition are produced, chemical plant and oil refinery effluent, urban sewage, sewage, mud or the like.This just means that the present invention's method can contain ammonium nitrate wastewater with processing and handle above-mentioned those waste water together.
The present invention's method can be handled and contain high density NH 4NO 3Waste water, and can improve its treatment effect, can make NH + 4Ion and NO - 3Ionic concentration obviously reduces.Based on this advantage, method of the present invention is only by means of simple equipment, just can handle easily by uranium ore processing to become nuclear fuel and by the NH that aftertreatment produced that used uranium fuel 4NO 3Concentration is 10% or higher waste water.
To be described by following example and comparative example about detailed content of the present invention.
Example 1
In one 300 milliliters stainless steel autoclave, add 100 milliliters of pH and be 10, NH 4NO 3Concentration is 10%(NH + 4-N/NO - 3-N=1) waste water was 250 ℃ of following thermolysiss 60 minutes.Give in the used air of autoclave supercharging, contained oxygen is approximately 0.01 times of theoretical amount.The ruthenium catalyst of 10 grams by titanium dioxide granule institute carrier band is housed in this still, and its granularity is 5 millimeters, presses titanium dioxide weight and calculates, and the amount of ruthenium is 2%.
NH + 4Ion, NO - 3The decomposition percentage ratio of ion and total nitrogen component is together with the table 1 that the results are shown in of example 2.
Table 1
Example 1 example 2
Catalyst activity sexual element Ru Pb
The pH 10 10 of waste water
NH 4NO 3Concentration (%) 10 10
NH + 4Rate of decomposition (%) 98 92
NO - 3Rate of decomposition (%) 75 80
The rate of decomposition of total nitrogen component (%) 87 86
Example 2
The thermolysis process of wastewater treatment is with example 1, and just the used catalyzer of this example is that its granularity is 5 millimeters by the palladium of titanium dioxide granule institute carrier band, presses titanium dioxide weight and calculates, and the amount of palladium is a 1%(weight).
Example 3
Adding 100 milliliters of pH in one 300 milliliters stainless steel autoclave is 10, NH 4NO 3Concentration is 1%(NH + 4-N/NO - 3-N=1) waste water was 250 ℃ of following thermal decomposition process 60 minutes.Oxygen level is about 0.2 times of theoretical amount in the air of supplying with.Add the ruthenium-containing catalyst of 10 grams by titanium dioxide institute carrier band in above-mentioned used autoclave, its granularity is 5 millimeters, and by titanium dioxide weight, the amount of ruthenium is a 2%(weight).
NH + 4Ion, NO - 3The rate of decomposition of ion and total nitrogen component is together with the table 2 that the results are shown in of example 4 to 12 and comparative example 1 and 2.
Table 2
Catalyst n H + 4-N/ NH + 4Branch NO - 3Branch total nitrogen component
The instance number active NO - 3-N the rate of separating is separated the rate rate of decomposition
(%) (%) (%) for composition (mol ratio)
3 Ru 1 81 42 63
4 Ru 1.3 97 83 91
5 Ru 1.9 98 89 95
6 Ru 2.8 96 81 93
7 Ru 3.9 93 86 93
8 Pd 1.0 87 50 70
9 Pd 1.3 97 80 90
10 Pd 1.9 98 95 97
11 Pd 2.8 96 97 97
12 Pd 3.9 96 95 96
Relatively
Routine number
1 does not have 1.9 5.0 0.8 6.9
2 pure titanium dioxide 1.9 5.2 0.8 7.1
Titanium carrier
Example 4 to 7
NH with predetermined amount 4OH be added to as example 3 used contain NH 4NO 3Waste water of the same race in, regulate NH + 4-N/NO - 3The mol ratio of-N, and handle this mixed solution by thermolysis process identical in the example 3.
Example 8
Press thermolysis process identical in the example 3 and handle waste water, be used catalyzer be the ruthenium that has replaced the titanium dioxide carrier band with the palladium of titanium dioxide granule carrier band, its granularity is 5 millimeters, by titanium dioxide weight, the amount of palladium is a 2%(weight).
Example 9 to 12
Contain NH with example 4 to 7 described same thermolysis process processing 4NO 3Waste water, only being to use strictly according to the facts, example 8 used palladium catalysts of the same race have replaced ruthenium catalyst.
Comparative example 1
Contain NH with example 5 same thermolysis process processing 4NO 3Waste water, just without catalyzer.
Comparative example 2
Contain NH with example 5 identical thermolysis process processing 4NO 3Waste water, just adopting diameter is the ruthenium that 5 millimeters pearl titanium dioxide of establishing the carrier band active ingredient have replaced this carrier institute carrier band.
Example 13 to 16
Handle waste water with the identical thermolysis process described in the example 3, just change NH 4NO 3Concentration and change pH value, it the results are shown in table 3.
Example 17 to 19
Press example 8 identical thermolysis process and handle waste water, just changed NH 4NO 3Concentration and pH value, it the results are shown in table 3.
Table 3
Catalyst n H 4NO 3NH + 4Divide NO - 3Divide the total nitrogen component
The instance number wastewater pH active concentration rate of separating is separated the rate rate of decomposition
(%) (%) (%) for composition (%)
13 5.3 Ru 1 64 50 59
14 5.0 Ru 4 are greater than 99 67 84
15 4.9 Ru 7 96 65 82
16 4.8 Ru 10 99 66 84
17 5.3 Pd 1 are greater than 99 64 83
18 5.0 Pd 4 86 50 69
19 4.9 Pd 7 88 40 66
Example 20
With pH be 10, NH 4NO 3Concentration is 10%(NH + 4-N/NO - 3-N=1.88) waste water adds from cylindrical nickelic stainless steel reactor bottom, with thermal decomposition method it is handled, reinforced air speed be 0.92 liter/hour (calculating) by free column volume simultaneously air with per hour 17.1 liters air speed (calculating) autoreactor bottom importing by the free column volume under the standard state.The mass velocity of liquid is 1.2 tons/meter 2Hour.Import airborne oxygen level and be about 0.24 times of theoretical amount.Dose the pearl palladium-containing catalyst by the titanium dioxide granule carrier band in the above-mentioned reactor, its granular size is 5 millimeters, and by titanium dioxide weight, the amount of palladium is a 2%(weight).Carrying out the pyrolysated temperature is 250 ℃, and pressure is 70 kilograms per centimeter 2
Liquid-gas mixture that reaction is produced enters liquid-gas separator after recovery of heat, liquid and gas are separated, through leaving system respectively after the cooling indirectly.
NH + 4, NO - 3List in table 4 with the decomposition percentage of total nitrogen component.
Do not detect NO in the gas phase xAnd SO x
Table 4
NH + 4Rate of decomposition (%) 99
NO - 3Rate of decomposition (%) is greater than 99
Total nitrogen component rate of decomposition (%) is greater than 99
Example 21
Press COD component and NO - 3The mol ratio of-N is 1: 2 a ratio, with C 6H 5OH joins in the pending waste water as the COD component.In one 300 milliliters stainless steel autoclave, add 100 milliliters of pH and be 10, NH 4NO 3Concentration is 1%(NH + 4-N/NO - 3-N=1) waste water carried out thermal decomposition process 60 minutes to it under 250 ℃.Add airborne oxygen level and be about 0.2 times of theoretical amount.Be filled with the ruthenium-containing catalyst of 10 grams by the titanium dioxide granule carrier band in this autoclave, its granularity is 5 millimeters, and by titanium dioxide weight, the amount of ruthenium is a 2%(weight).
NH + 4Ion, NO - 3The decomposition percentage of ion and total nitrogen component is listed in table 5 together with the result one of example 22 to 26.(seeing the 12nd page)
Example 22 and 23
C with predetermined amount 6H 5OH joins and contains NH 4NO 3Waste water in, to regulate C 6H 5OH/NO - 3The mol ratio of-N, the pH value of this waste water, NH 4NO 3Concentration is different with example 21 all.Handle this mixed solution with example 21 described identical thermolysis process.
Example 24
Handle waste water with example 21 identical methods, just catalyzer employing granularity is 5 millimeters
Figure 86102728_IMG1
Figure 86102728_IMG2
The palladium of titanium dioxide carrier band replaced the ruthenium of its institute's carrier band, by titanium dioxide weight, the amount of palladium is a 2%(weight).
Example 25 and 26
Handle waste water with the thermolysis process that example 22 is identical with 23, just adopt to have replaced ruthenium catalyst as example 24 used palladium-containing catalysts of the same race.
Example 27 to 29
With C 6H 5OH and NH 4OH is added to and contains NH 4NO 3Waste water in, this mixed solution of thermolysis under the condition identical with example 21.
In example 27 and 28, with sodium hydroxide pH is transferred to designated value, its pH value is not done adjusting in example 29.
The results are shown in table 6.(seeing the 13rd page)
Example 30 to 32
With C 6H 5OH and NH 4OH is added to and contains NH 4NO 3Waste water in, this mixed solution of thermolysis under the condition identical with example 24.
In example 30 and 31, pH is transferred to designated value, and does not transfer pH in the example 32 with sodium hydroxide.
The results are shown in table 6.(seeing the 13rd page)
Example 33
At NH 4NO 3Concentration is 10%(NH + 4-N/NO - 3In-N=1.88) the waste water, press COD component and NO - 3The mol ratio of-N is about 1: 2 ratio and adds C as the COD component 6H 5OH transfers to 10 with aqueous sodium hydroxide solution with the pH of this mixture.The mixed solution that the produces air speed with 0.95 liter/hour (calculating with free column volume) is added from cylindrical nickelic stainless steel reactor bottom, with thermal decomposition method it is handled, air then feeds from this reactor lower part with the air speed of 18.5 liters/hour (under standard state, calculating with free column volume).The mass velocity of liquid is 2.43 tons/meter 2Hour.Oxygen level is about 0.4 times of theoretical amount in the air supply.Dose pearl shape palladium catalyst in this reactor, palladium catalyst is to be 5 millimeters titanium dioxide granule carrier band by granularity, and by titanium dioxide weight, the amount of palladium is a 2%(weight).The temperature of carrying out pyrolysis is 250 ℃, and pressure is 70 kilograms per centimeter 2
The liquid that reaction produces-gas mixture enters liquid-gas separator through after the heat recuperation, and gas and liquid are separated, and leaves reactive system respectively after the cooling indirectly.
NH + 4, NO - 3List in table 7 with the decomposition percentage of total nitrogen component.
Do not detect NO in the gas phase xAnd SO x
Table 7
NH + 4Rate of decomposition (%) is more than 99
NO - 3Rate of decomposition (%) is more than 99
Total nitrogen component rate of decomposition (%) is more than 99
COD component rate of decomposition (%) is more than 99

Claims (46)

1, a kind of treatment process that contains ammonium nitrate wastewater, this method is to make waste water generation wet method thermolysis effect in the presence of by carrier carried catalyzer, said catalyzer comprises the insoluble or compound that is slightly soluble in water of at least a precious metal or its as its active ingredient, the pH of waste water maintains about 3 to about 11.5 scopes, and heat decomposition temperature is about 100 to about 370 ℃.
2, the method for claim 1, wherein said waste water are to be approximately 5 to about 11 scope at pH, make it to take place wet method thermolysis effect.
3, the method for claim 1, wherein said catalyst activity sexual element comprises at least a following element, i.e. ruthenium, rhodium, palladium, osmium, iridium, platinum and gold.
4, the method for claim 1, wherein said catalyst activity sexual element comprise the insoluble of at least a following element or are slightly soluble in the compound of water, and these elements are ruthenium, rhodium, palladium, osmium, iridium, platinum and gold.
5, method as claimed in claim 4, wherein said catalyst activity sexual element comprises at least a following compound, i.e. ruthenous chloride, platinum dichloride, sulfuration ruthenium and rhodium sulphide.
6, the method for claim 1, wherein said wet method thermolysis is carried out in fixed-bed type reactor.
7, the method for claim 1, wherein said wet method thermolysis is carried out in fluid bed-type of reactor.
8, the method for claim 1, wherein said wet method thermolysis are to carry out to about 300 ℃ temperature about 200.
9, a kind of processing contains the method for ammonium nitrate wastewater, this method comprises makes waste water stand the wet method pyrolysis under the following conditions: (ⅰ) in the presence of by carrier carried catalyzer, it is insoluble or be slightly soluble in the active ingredient of the compound of water as it that this catalyzer contains at least a precious metal or its; (ⅱ) be lower than in the presence of the oxygen of theoretical amount, said theoretical amount oxygen is meant that with the ammonia in the waste water, organism and inorganic substance are decomposed into N 2, H 2O and CO 2Required oxygen amount; Make the pH of waste water be maintained at about 3 to about 11.5 scopes simultaneously, temperature is about 100 to about 370 ℃.
10, method as claimed in claim 9, wherein said waste water are to be to stand the wet method pyrolysated between about 5 to about 11 at pH.
11, as method as described in the claim 9, wherein said catalyst activity sexual element is at least a following element, i.e. ruthenium, rhodium, palladium, osmium, iridium, platinum and gold.
12, method as claimed in claim 9, wherein said catalyst activity sexual element comprise at least a insoluble or be slightly soluble in the precious metal chemical complex of water, and said precious metal is meant ruthenium, rhodium, palladium, osmium, iridium, platinum and gold.
13, method as claimed in claim 12, wherein said catalyst activity sexual element comprises at least a following compound, i.e. ruthenous chloride, platinum dichloride, sulfuration ruthenium and rhodium sulphide.
14, method as claimed in claim 9, wherein said wet method thermolysis is carried out in fixed-bed type reactor.
15, method as claimed in claim 9, wherein said wet method thermolysis is carried out in fluid bed-type of reactor.
16, method as claimed in claim 9, wherein said wet method thermolysis are to carry out to about 300 ℃ temperature about 200.
17, method as claimed in claim 9, wherein said oxygen-containing gas are to add with 0.2 to 0.6 times of about theoretical oxygen amount amount.
18, a kind of treatment process that contains ammonium nitrate wastewater, this method comprise that adding mol ratio in the waste water is 1＜NH + 4-N/NO - 3The ammonia amount of-N≤5 makes this waste water carry out the wet method thermolysis under the following conditions: (ⅰ) in the presence of by carrier carried catalyzer, this catalyzer contains the insoluble or compound that is slightly soluble in water of at least a precious metal or its as its active ingredient; (ⅱ) be lower than in the presence of the oxygen of theoretical requirement, the oxygen of said theoretical requirement is meant that the ammonia in the waste water, organism and inorganic substance are decomposed into N 2, H 2O and CO 2Required oxygen amount; Simultaneously the pH of waste water maintains about 3 to about 11.5, and temperature is about 100 to about 370 ℃.
19, method as claimed in claim 18, wherein said waste water are to be to carry out the wet method pyrolysated under about about 5 to 11 at pH.
20, method as claimed in claim 18, wherein said catalyst activity sexual element comprises at least a following element, i.e. ruthenium, rhodium, palladium, osmium, iridium, platinum and gold.
21, method as claimed in claim 18, wherein said catalyst activity sexual element comprise at least a insoluble or be slightly soluble in the precious metal chemical complex of water, and said precious metal is meant ruthenium, rhodium, palladium, osmium, iridium, platinum and gold.
22, method as claimed in claim 21, wherein said catalyst activity sexual element comprises at least a following compound, i.e. ruthenous chloride, platinum dichloride, sulfuration ruthenium and rhodium sulphide.
23, method as claimed in claim 18, wherein said wet method thermolysis is carried out in fixed-bed type reactor.
24, method as claimed in claim 18, wherein said wet method thermolysis is carried out in fluid bed-type of reactor.
25, method as claimed in claim 18, wherein said wet method thermolysis are to carry out to about 300 ℃ temperature about 200.
26, method as claimed in claim 18, wherein said oxygen-containing gas are to add to about about 0.6 times oxygen amount with about 0.2 of theoretical oxygen amount.
27, a kind of processing contains the method for ammonium nitrate wastewater, and this method comprises in waste water adds every mole of NO - 3The COD component that ion is no more than 1 mole, carry out the wet method thermal decomposition process of waste water under the following conditions: (ⅰ) in the presence of by carrier carried catalyzer, this catalyzer contains the insoluble or compound that is slightly soluble in water of at least a precious metal or its as the activity of such catalysts composition; (ⅱ) be lower than in the presence of the oxygen of theoretical requirement, so-called theoretical oxygen demand is meant that with the ammonia in the waste water, organism and inorganic substance are decomposed into N 2, H 2O and CO 2Required oxygen amount; Simultaneously the pH of waste water maintains about 3 to about 11.5, and temperature is about 100 to about 370 ℃.
28, method as claimed in claim 27, wherein said waste water are to carry out the wet method pyrolysated under about pH is about 5 to 11.
29, method as claimed in claim 27, wherein said catalyst activity sexual element comprises at least a following element, i.e. ruthenium, rhodium, palladium, osmium, iridium, platinum and gold.
30, method as claimed in claim 27, wherein said catalyst activity sexual element comprise at least a insoluble or be slightly soluble in the precious metal chemical complex of water, and said precious metal is meant ruthenium, rhodium, palladium, osmium, iridium, platinum and gold.
31, method as claimed in claim 30, wherein said catalyst activity sexual element comprises at least a following compound, i.e. ruthenous chloride, platinum dichloride, sulfuration ruthenium and rhodium sulphide.
32, method as claimed in claim 27, wherein said wet method thermolysis is carried out in fixed-bed type reactor.
33, as the method as described in the claim 27, wherein said wet method thermolysis is carried out in fluid bed-type of reactor.
34, method as claimed in claim 27, wherein said wet method thermolysis is carried out under about 200 to 300 ℃ of left and right sides temperature.
35, method as claimed in claim 27, wherein oxygen-containing gas approximately is to add to about 0.6 times amount with 0.2 of theoretical oxygen amount.
36, method as claimed in claim 27, wherein every mole of NO - 3Ionic COD component add-on is about 0.1 to about 0.5 mole.
37, a kind of treatment process that contains ammonium nitrate wastewater, this method comprise in waste water adds every mole of NO - 3COD component that ion is no more than 1 mole and mol ratio are 1＜NH + 4-N/NO - 3The ammonia amount of-N≤5, and carry out the wet method thermal decomposition process of waste water under the following conditions: (ⅰ) in the presence of by carrier carried catalyzer, it is insoluble or be slightly soluble in the active ingredient of the compound of water as it that this catalyzer contains at least a precious metal or its; (ⅱ) be lower than in the presence of the oxygen of theoretical amount, said theoretical amount oxygen is meant that with the ammonia in the waste water, organism and inorganic substance are decomposed into N 2, N 2O and CO 2Required oxygen amount; The pN of waste water is maintained at about about 3 to 11.5 simultaneously, and temperature is about about 100 to 370 ℃.
38, method as claimed in claim 37, wherein said waste water are to be to carry out the wet method pyrolysated under about about 5 to 11 at pH.
39, method as claimed in claim 37, wherein said catalyst activity sexual element comprises at least a precious metal, i.e. ruthenium, rhodium, palladium, osmium, iridium, platinum and gold.
40, method as claimed in claim 37, wherein said catalyst activity sexual element comprise at least a insoluble or be slightly soluble in the precious metal chemical complex of water, and said precious metal is meant ruthenium, rhodium, palladium, osmium, iridium, platinum and gold.
41, method as claimed in claim 40, wherein said catalyst activity sexual element comprises at least a following compound, i.e. ruthenous chloride, platinum dichloride, sulfuration ruthenium and rhodium sulphide.
42, method as claimed in claim 37, wherein said wet method thermolysis is carried out in fixed-bed type reactor.
43, method as claimed in claim 37, wherein said wet method thermolysis is carried out in fluid bed-type of reactor.
44, method as claimed in claim 37, wherein said wet method thermolysis are to carry out under about about 200 to 300 ℃ temperature.
45, method as claimed in claim 37, wherein said oxygen-containing gas are to add to about 0.6 times amount with about 0.2 of theoretical oxygen amount.
46, method as claimed in claim 37, wherein said COD component add-on is every mole of NO - 3The COD that ion is about 0.1 to 0.5 mole.
CN86102728A 1985-03-28 1986-03-28 Process for treating ammonium nitrate-centg. waste water Expired CN1012570B (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP64228/85 1985-03-28
JP64227/85 1985-03-28
JP64229/85 1985-03-28
JP60064227A JPH0645025B2 (en) 1985-03-28 1985-03-28 Method of treating wastewater containing ammonium nitrate
JP60064228A JPH0645026B2 (en) 1985-03-28 1985-03-28 Method of treating wastewater containing ammonium nitrate
JP60064229A JPH0647100B2 (en) 1985-03-28 1985-03-28 Method of treating wastewater containing ammonium nitrate

Publications (2)

Publication Number Publication Date
CN86102728A CN86102728A (en) 1986-10-01
CN1012570B true CN1012570B (en) 1991-05-08

Family

ID=27298419

Family Applications (1)

Application Number Title Priority Date Filing Date
CN86102728A Expired CN1012570B (en) 1985-03-28 1986-03-28 Process for treating ammonium nitrate-centg. waste water

Country Status (5)

Country Link
US (1) US4654149A (en)
EP (1) EP0196597B1 (en)
CN (1) CN1012570B (en)
CA (1) CA1275511C (en)
DE (1) DE3685674T2 (en)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4699720A (en) * 1985-03-12 1987-10-13 Osaka Gas Company Limited Process for treating waste water by wet oxidations
DE3906781A1 (en) * 1989-03-03 1990-09-06 Gutec Gmbh Process for reducing the nitrite content and/or nitrate content in water to ammonium
JP2628089B2 (en) * 1989-08-18 1997-07-09 大阪瓦斯株式会社 Wastewater treatment method
US5221486A (en) * 1991-04-12 1993-06-22 Battelle Memorial Institute Aqueous phase removal of nitrogen from nitrogen compounds
US5433868A (en) * 1993-09-09 1995-07-18 Battelle Memorial Institute Sewage treatment method
FR2726262B1 (en) * 1994-10-27 1998-06-26 Omnium Traitement Valorisa METHOD AND PLANT FOR TREATING EFFLUENTS BY OXIDATION IN THE PRESENCE OF A HETEROGENEOUS CATALYST
FR2726261B1 (en) * 1994-10-27 1997-01-17 Omnium Traitement Valorisa PROCESS AND INSTALLATION FOR TREATMENT OF EFFLUENTS BY OXIDATION IN THE PRESENCE OF A HETEROGENIC CATALYST
US5785868A (en) * 1995-09-11 1998-07-28 Board Of Regents, Univ. Of Texas System Method for selective separation of products at hydrothermal conditions
FR2781783B1 (en) * 1998-07-28 2000-12-08 Commissariat Energie Atomique PROCESS FOR REDUCING THE CONCENTRATION OF NITRATES AND / OR NITRIC ACID OF AN AQUEOUS SOLUTION
US6759014B2 (en) * 2001-01-26 2004-07-06 Symyx Technologies, Inc. Apparatus and methods for parallel processing of multiple reaction mixtures
US6332986B1 (en) 2000-07-10 2001-12-25 Air Products And Chemicals, Inc. Treatment of water containing organic wastes with ammonium nitrate
US6379562B1 (en) * 2001-03-21 2002-04-30 Atr Products And Chemicals, Inc. Treatment of water containing organic wastes with aromatic amine nitrate salts
US20080053909A1 (en) * 2006-09-06 2008-03-06 Fassbender Alexander G Ammonia recovery process
US20080053913A1 (en) * 2006-09-06 2008-03-06 Fassbender Alexander G Nutrient recovery process
US20080156726A1 (en) * 2006-09-06 2008-07-03 Fassbender Alexander G Integrating recycle stream ammonia treatment with biological nutrient removal
CN112480971B (en) * 2020-10-28 2022-10-11 中石化宁波工程有限公司 Control method of pulverized coal gasification process for co-combustion of high-concentration organic waste liquid
CN114409166B (en) * 2022-01-25 2023-05-23 浙江工业大学 Method for treating ammonium nitrate wastewater by catalytic wet oxidation-ammonification
CN115779897B (en) * 2022-11-28 2024-05-24 青岛科技大学 Preparation and application of bimetallic nano material for degrading organic pollutants in water by using electrocatalytic reaction

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5919757B2 (en) * 1976-08-10 1984-05-08 大阪瓦斯株式会社 Wastewater treatment method
JPS53102866A (en) * 1977-02-21 1978-09-07 Shokubai Kasei Kogyo Kk Treating method for waste gas comtaining ammonia
JPS5929317B2 (en) * 1979-05-16 1984-07-19 大阪瓦斯株式会社 Wastewater treatment method
DE2938654B1 (en) * 1979-09-25 1980-09-18 Didier Eng Process for the destruction of ammonia in waste water
DE3048002C2 (en) * 1980-12-19 1985-09-19 Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe Process for removing ammonium nitrate from aqueous solutions
DE3243840A1 (en) * 1982-11-26 1984-05-30 Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe METHOD FOR DENITITATING AQUEOUS, NITRIC ACID, SALTY WASTE SOLUTIONS

Also Published As

Publication number Publication date
US4654149A (en) 1987-03-31
CA1275511C (en) 1990-10-23
DE3685674T2 (en) 1993-01-28
CN86102728A (en) 1986-10-01
EP0196597A2 (en) 1986-10-08
DE3685674D1 (en) 1992-07-23
EP0196597A3 (en) 1988-07-27
EP0196597B1 (en) 1992-06-17

Similar Documents

Publication Publication Date Title
CN1012570B (en) Process for treating ammonium nitrate-centg. waste water
CN1029833C (en) Process for treating waste water
EP0224905B1 (en) Process for treating waste water by wet oxidations
AU600666B2 (en) Electrolytic dissolution and recovery of noble metals
CN101045204A (en) Catalyst for wastewater treatment and method for wastewater treatment using said catalyst
CN1108866C (en) ZnS photocatalyst, preparation thereof and use thereof the producing hydrogen
CN1319880C (en) Treatment method for sewage
CN100336735C (en) Method and apparatus for treating high concentrated organic wastewater by hydrothermal electrical catalytic oxidation
CN1699174A (en) Method for regenerating sodium cyanide from solutions containing cyanogen and thiocyanate
CN1072174A (en) The reaction zone that adopts different productive rates is with the method for production urea and used device thereof
CN1153774A (en) Preparation method of thiocarbamate compound
CN1078591C (en) Process for preparing trioxane
CN1242939C (en) Process for treating chloroform and carbon tetrachloride industrial waste water by catalytic metal reduction-flocculating settling method
JPH0691992B2 (en) Treatment method of wastewater containing high concentration ammonium nitrate
JPH11300374A (en) Treatment of waste water
JP2969477B2 (en) Treatment method for wastewater containing ammonium nitrate
JP2969467B2 (en) Treatment method for wastewater containing ammonium nitrate
JP2969478B2 (en) Treatment method for wastewater containing ammonium nitrate
CN1202388A (en) Method for desulfurating by bauxite
CN1186484A (en) Process for producing cyclohexanonoxim and caprolactam
JP2899719B2 (en) Treatment method for wastewater containing ammonium nitrate
JPH0645028B2 (en) Method of treating wastewater containing ammonium nitrate
JP2627953B2 (en) Wastewater treatment method
JPH0645026B2 (en) Method of treating wastewater containing ammonium nitrate
JPH0716663B2 (en) Treatment method of wastewater containing high concentration ammonium nitrate

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C13 Decision
GR02 Examined patent application
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CX01 Expiry of patent term